Environ. Sci. Technol. 2004, 38, 5939-5949
SugarssDominant Water-Soluble Organic Compounds in Soils and Characterization as Tracers in Atmospheric Particulate Matter ,†,‡,§
BERND R. T. SIMONEIT,* V L A D I M I R O . E L I A S , †,# MINORU KOBAYASHI,§ KIMITAKA KAWAMURA,§ AHMED I. RUSHDI,† P A T R I C I A M . M E D E I R O S , †,‡ WOLFGANG F. ROGGE,| AND BORYS M. DIDYK⊥ College of Oceanic & Atmospheric Sciences, Oregon State University, Corvallis, Oregon 97331-5503, Environmental Sciences Graduate Program, Oregon State University, Corvallis, Oregon 97331-2904, Institute of Low-Temperature Science, N19W8, Hokkaido University, Kita-ku, Sapporo 060-0819, Japan, Department of Civil and Environmental Engineering, Florida International University, Miami, Florida 33199, and Refineria de Petroleo, Concon, Chile
The presence of saccharides is being reported for aerosols taken in urban, rural, and marine locales. The commonly found primary saccharides are R- and β-glucose, R- and β-fructose, sucrose, and mycose with lesser amounts of other monosaccharides. Saccharide polyols are also found in some airsheds and consist mainly of sorbitol, xylitol, mannitol, erythritol, and glycerol. In temperate climate areas these compounds increase from negligible concentrations in winter aerosols (usually dominated by levoglucosan and related anhydrosaccharides from biomass burning) to a maximum in late spring-summer, followed by a decrease to winter. The composition of the saccharide mixtures suggests soil and associated microbiota as the source. Saccharide analyses of soils confirmed these compositions. Therefore, we propose resuspension of soil (also unpaved road dust) from agricultural activities as a major component of aerosol particles and the saccharides are the source specific tracers. In addition, the saccharides as well as the anhydrosaccharide derivatives from biomass burning are completely water soluble and thus contribute significantly to the total water-soluble mass of aerosols.
Introduction Currently there are two new research directions on particulate matter in the atmosphere. One is the organic compound * Corresponding author phone: (541)737-2155; fax: (541)737-2064; e-mail:
[email protected]. † College of Oceanic & Atmospheric Sciences, Oregon State University. ‡ Environmental Sciences Graduate Program, Oregon State University. § Hokkaido University. # Present address: Analytical Solutions, P. Saldanha 115, Jardim Botaˆnico 22461-220, Rio de Janeiro, Brazil. | Florida International University. ⊥ Refineria de Petroleo. 10.1021/es0403099 CCC: $27.50 Published on Web 10/09/2004
2004 American Chemical Society
composition of the polar water-soluble fraction of atmospheric aerosols (1-3). The second is the contributions and source strengths of soil and desert dusts to the atmosphere of urban, rural, and global regions (e.g., refs 4 and 5).
Water-Soluble Organic Compounds The water-soluble organic matter documented for aerosol particles consists of short-chain dicarboxylic acids, anhydrosaccharides from biomass burning (e.g., levoglucosan), saccharides, and to some extent phenolics. Oxalic acid, with the other short-chain homologues of dicarboxylic, hydroxydicarboxylic, aromatic dicarboxylic, oxocarboxylic, and hydroxycarboxylic acids, have been reported as major watersoluble components of aerosols (e.g., refs 6-8). Most of these carboxylic acids are secondary oxidation products of atmospheric organic compounds and are found in remote marine as well as continental rural to urban areas (e.g., ref 9). The tracers for emissions from biomass burning, primarily levoglucosan from cellulose decomposition, with lesser amounts of mannosan, galactosan, and 1,6-anhydroglucofuranose, are also common aerosol components (10-12). These anhydrosaccharides are completely soluble in water and have been reported globally in remote to urban air sheds (e.g., Table 1 (3, 13-18)). Lignin, another major biopolymer of wood, yields phenolic tracers upon burning in the smoke characteristic of the fuel type (19-24). These tracers (e.g., vanillic acid) are not completely water soluble, although phenolics are hygroscopic. Major amounts of saccharides (Table 1) have been reported to be present in aerosols of certain geographic regions such as Amazonia, Brazil (3), northwestern Pacific with Korea and Japan (11), and Santiago, Chile (25, 26). The dominant primary saccharides consist of R- and β-glucose, R- and β-fructose, sucrose, and mycose (trehalose), with lesser amounts of inositols, R- and β-mannose, R- and β-xylose, and R- and β-galactose. In addition, saccharide polyols (alditols, i.e., reduced sugars) are also found and include sorbitol (D-glucitol), xylitol, mannitol, arabitol, erythritol, and glycerol (3, 11). All these saccharides are emitted directly from sources, although they may also be emitted significantly by thermal stripping during burning in wildfires. These saccharides are completely soluble in water. Thus, their specific sources need to be characterized.
Soil Organic Compounds There is a need to demonstrate potential organic tracers that are unique to soil to complement the diverse mineral and trace metal compositions of soils. Soil is a complex mixture of inorganic and organic material. Plant detritus is considered to be the major source for soil organic matter (27). Depending on the geographical location, agricultural soil may contain 5-6% of organic matter, sandy soil less than 1%, and poorly drained soils about 10%. Soil organic matter is composed of a mixture of aerial and below-ground plant litter, animal and microbial residues, lipids, carbohydrates, peptides, cellulose, lignin, and humic material (27). About 5-20% of the soil organic matter is composed of carbohydrates and up to 10% of lipids, phytosterols, and other compounds (27). Plant detritus associated with soil is composed of “above” and “below” ground plant parts. Plant cuticles “above” and “below” ground are waterproof barriers, protecting epidermal cells of leaves, fruits, roots, and nonwoody stems with a waxlike surface layer made of lipids and biopolymers. These plant waxes consist of higher molecular weight alkanes, alkanols, wax esters, alkanoic acids, alkanals, and to a minor VOL. 38, NO. 22, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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TABLE 1. Concentrations of Major Saccharides in Aerosols compounda
Santiago, Chilec
Kuala Lumpur, Malaysiac
Sapporo, Japanc
Ghent, Belgiumd
Rondoˆ nia, Brazile
various locales, U.S.A.f
levoglucosan 12-2452 (839) 1162-33400 (14460) 6-56 121-1133 (477) 1182-6900 (2460) 500-2980 (1450) mannosan 1-233 (81) 154-4430 (1422) 0.2-15 17-153 (66) 6-371 (126) 170-322 galactosan 1.7-127 (45) 84-2410 (1014) 0.6-2.4 4-44 (20) 2-148 (55) 96-144 1,6-anhydrogluco- 0.5-195 (62) 135-4005 (1520) 5-248 (82) furanose glucoseb 10-2210 (940) 1-34 14-62 (37) 10-15 fructoseb 12 3-20 (9) galactoseb 0.2-2.4 (0.9) mannoseb 48-6800 (2053) 0.6-4 (2) 9-13 1-33 (13) 9-17 xyloseb sorbitol 3-26 0-1.7 (0.8) mannitol 10-50 (26) xylitol 2-22 erythritol 2-39 (16) glycerol 3-24 0.5-9 (3) inositols 3-104 0.5-21 (8) sucrose 15-3060(1108) 0.4-9 0.8-26 (7) 3.2-4 maltose 6-2390 (622) 2-550 (130) 3-4 mycose 8-1660 (477) 0.2-12 5-18 (9)
Datong, P. R. Chinac 1350 108 106
102
1148 68 54
a Concentrations are given as ng/m3, numbers in parentheses are the mean. b Both R- and β-isomers are summed. c This work (all TSP). d Reference 16 - sampled during winter (PM10). e Reference 3 - sampled during October (PM10 and PM2.5). f References 14, 15, and 54 - all PM10.
extent alkanediols, aldehydes, and other biomarker compounds (28, 29). The aerial plant parts contain cutin, and the underground plant roots and tubes are comprised of suberin, both biopolyesters (30). In addition, all plants contain cellulose, and woody plants have lignin under the polyester outer sheaths. Cutin biopolyester is composed of ω-hydroxy and epoxy fatty acids, whereas suberin includes aromatics with polyesters. All lipids and biopolymers are biodegraded over time in soils. Active soil contains a few million bacteria, up to a million actinomycetes, and several thousand fungi per gram. Therefore, microorganisms contribute lipids to the soil organic matter, including fatty acids, fatty alcohols, and hydrocarbons as well as utilize and alter the lipid pool. When compared to epicuticular plant waxes, lipids of lower molecular weight (eC20) found in soil have been suggested to be mainly of a microbial origin (31-34). Over time, vascular plant material undergoes diagenic degradation caused by heterotrophic microorganisms (35) as well as heterogeneous chemical reactions on minerals contained in soil (36). Thus, the compositions of the lipid and polar fractions found in soil depend on plant growth, biochemical and physical soil properties, level of cultivation, location, and climatic conditions. It should be pointed out that ergosterol is used in soil science as the tracer for fungal biomass (37-39). It occurs in these soil extracts as a trace component among the other sterols and may be utilized as a confirming tracer for the fungal component of soils. Therefore, stable and distinct molecular markers or an assemblage of such organic compounds are needed in order to trace the release of soil dust from the ground into the atmosphere. The half-life, i.e., chemical stability, of molecular markers required for source-receptor modeling must be adequate to exceed the particular residence time of air masses within the modeling area. Furthermore, the group of individual organic compounds or series of homologues must have a concentration pattern that is characteristic of the source under consideration. Soil input to the atmosphere occurs by wind erosion and resuspension from anthropogenic activities in numerous ways. Natural wind erosion introduces surface fines from deserts, dried lakes and washes, denuded lands, and fallow agricultural fields. Resuspension of dirt and soil from human activities include agricultural tilling, husbandry and harvesting, construction engineering projects, and traffic on unpaved 5940
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roads. The organic and inorganic tracer compositions of soil samples from some of these input sources are being characterized (e.g., refs 40-43). Here we demonstrate the utility of saccharides as organic tracers for soil input to the atmosphere and thus their major contribution to the water-soluble organic fraction of the particulate matter of impacted airsheds. The sources, chemistry, and quantitation of saccharide tracers will be described here in detail, so that they may be applied in source models.
Experimental Methods Samples. Soil samples were taken by scraping the surface fines (dry) from various active and fallow agricultural fields and natural areas. The samples (∼5 g) were dried in an oven at 40 °C and then sieved ( 99% for both cases. Thus, the anhydrosaccharides are useful tracers for smoke from biomass burning while associated with the aerosol particle matrices. The saccharides likewise are associated with and encapsulated in particles and, therefore, are less prone to degradation. Serial dilutions of standard anhydrosaccharides, saccharides, and fatty acids were prepared and analyzed for recovery and GC-MS response factor determinations (1-200 µg mL-1). Recoveries of levoglucosan, glucose, sucrose, palmitic acid, and stearic acid when spiked onto quartz filters and extracted with the dichloromethane/methanol (1:1 v/v) mixture were better than 90% (44). Aerosol Saccharides. The saccharides in aerosol particulate matter are comprised of three groups: (a) the anhydro derivatives comprised mainly of levoglucosan (1,6-anhydroβ-D-glucopyranose, I, chemical structures are given in Chart I), with minor mannosan (II), galactosan (III), and 1,6anhydro-β-D-glucofuranose (levoglucosan isomer, IV); (b) the
grape orchard (temperate, summer)
tomato field (temperate, summer)
Toya, Hokkaido soil (winter)
unpaved road dust (temperate)
paved road dust (temperate)
CHART 1. Chemical Structures
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FIGURE 2. Representative examples of GC-MS data for silylated total extracts of atmospheric particulate matter: Santiago, Chile (winter 1991): (a) total ion current (TIC) trace, (b) m/z 204 and 361 key ion trace for mono- and disaccharides; Concon, Chile (suburban winter), (c) TIC trace, (d) m/z 204 and 361 key ion trace; Sapporo, Japan (June 28-July 5, 2001), (e) TIC trace, (f) m/z 204 and 361 key ion trace; (g) Datong, P. R. China (April, 1991) m/z 204 and 361 key ion trace; and (h) Sapporo, Japan (March 2002), total aqueous extract TIC trace. The saccharides and anhydrosaccharides are labeled, i4 ) n-alkanoic acids, iO ) n-alkanols, ib ) n-alkanes, C ) cholesterol, S ) sitosterol, G ) galactosan, Gf ) 1,6-anhydro-β-D-glucofuranose, M ) mannosan, VA ) vanillic acid, SA ) syringic acid, DHA ) dehydroabietic acid, P ) phthalate, X ) artifact from BSTFA, UCM ) unresolved complex mixture of branched and cyclic hydrocarbons. primary saccharides consisting of R- and β-glucose (V), Rand β-mannose (VI), inositols (VII), sucrose (VIII), and mycose (trehalose, IX); and (c) the saccharide polyols (alditols, i.e., reduced sugars) ranging from sorbitol (D-glucitol, X), mannitol (XI), xylitol (XII), arabitol (XIII), erythritol (XIV), to glycerol (XV). Minor amounts of other monosaccharides (e.g., xylose, fructose, galactose) are also found in some samples. Levoglucosan, with mannosan, galactosan, and 1,6anhydro-β-D-glucofuranose (I-IV) are the key tracers for smoke particulate matter from burning of biomass (i.e., thermal alteration products from mainly cellulose and lesser amounts of hemicellulose (10)). These compounds have been found in aerosols over the ocean and thus are stable during long-range transport (13, 14). They are detectable at ng/m3 levels in low-volume fine-particle aerosol samples in urban areas (e.g., refs 17 and 18) as well as in conventional aerosol particle samples taken in various global areas (e.g., refs 3, 10, 11, 15, 16, and 54).
The presence of the saccharide anhydrides (I-IV) is illustrated in Figure 2 for various aerosol samples. The dominant compound in smoke impacted air sheds is levoglucosan, as can be seen from the GC-MS data of the total silylated extracts from TSP filters (Figure 2a,c). The saccharides can also be extracted directly with water and immediately derivatized by silylation for GC-MS analysis. The saccharide anhydrides are stable to hydrolysis for brief time periods as is illustrated in Figure 2h. However, extended aqueous storage of extracts results in hydrolysis of the anhydrosaccharides. Therefore, the saccharide anhydro derivatives from biomass burning are tabulated with the corresponding data for the other carbohydrates (Table 1). The primary saccharides (e.g., glucose, sucrose, mycose, etc.) and the saccharide polyols (e.g., sorbitol, xylitol, etc.) are candidate tracers for surface soil dust and are discussed next. The dominant primary saccharides in aerosols are comprised of R- and β-glucose (V), sucrose (VIII), and mycose VOL. 38, NO. 22, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 3. Representative examples of GC-MS data for silylated total extracts of soils: Ducke Reserve, Amazonia, Brazil (summer)s(a) TIC trace, (b) m/z 204 and 361 key ion trace; Safflower field, San Joaquin Valley, California (summer)s(c) TIC trace, (d) m/z 204 and 361 key ion trace; and Toya, Hokkaido, Japan (early spring, fallow field)s(e) TIC trace, and (f) m/z 204 and 361 key ion trace. The saccharides are labeled, ai ) anteiso homolog, and numbers with symbols as in Figure 2. VOL. 38, NO. 22, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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(IX), with various other minor components (e.g., galactose, fructose, mannose, xylose, inositols, and maltose) at some locales (Table 1). The distributions of the silylated saccharides in aerosols are also shown in Figure 2, where the key ion plots of m/z 204 for the monosaccharides with m/z 361 for the disaccharides are given. The anhydrosaccharides also have the m/z 204 key ion. The ratio of R- to β-glucose is generally almost one, and thus the two isomers are summed for concentration reports. Sucrose (VIII) and mycose (IX) occur at varying ratios which may reflect source properties. Mycose and the reduced sugars are products of fungal metabolism (e.g., ref 33). In general, the saccharides are present at relatively low atmospheric concentrations during the early spring and become dominant into the summer season, paralleling the agricultural tilling practices which resuspend soil dust into the passing aerosols as, for example, on the Asian continent (11). Soil Saccharides. Saccharides are a major fraction of soil organic matter (55) and have also been characterized in riverine particulate matter (56). The saccharide content of soils is summarized in Table 2 and illustrated with some examples for a tropical soil from Amazonia, Brazil and two temperate soils from the San Joaquin Valley in California and the Toya area, Hokkaido, Japan (Figure 3). The tropical soil contains a complex mixture of mono- and disaccharides (167 µg/g), whereas the temperate examples have mainly glucose, sucrose, and mycose with minor inositol, rhamnose, arabinose, and lyxose. In winter and early spring, the saccharide content of soils is low because the living biomass is dormant (Figure 3e,f), especially in frozen terrain (0.28 µg/g). The sugars represent a significant proportion of the total organic extract of soils during the growing season (Figure 3a,c vs 3e). Various representative agricultural soils have been analyzed to determine their saccharide contents for source evaluation of soil resuspension into the atmosphere (42, 43). In general, R- and β-glucose, inositols, sucrose, and mycose are the common tracers to all samples analyzed (42, 43). Saccharide Contribution to Water-Soluble Compounds. The saccharides comprise from 13 to 26% of the total compound mass (TCM) identified in continental aerosols and have isolated higher values over the ocean (up to 63%, e.g., ref 11). We interpret these saccharides to represent viable biomass and extracellular organic matter mainly in soils but also in lesser amounts in road dust, dried lake sediments, etc., and possibly in marine particulate matter. Saccharides have been characterized in urban aerosols that contain entrained soil dust (e.g., ref 25) and in remote and rural areas (e.g., ref 3 and 11). Thus, they are proposed here as tracers for soil resuspension with associated microbiota from agricultural tilling and harvesting, wind erosion, or traffic. The water solubility of the carbonaceous organic fraction of aerosols is a major open question in climate models (2, 57). Oxalic acid, with the other short-chain dicarboxylic acids, have been documented as the dominant water-soluble components of organic aerosol matter (e.g., refs 7 and 8). Here we propose to add the following groups of organic compounds to the list of water-soluble organic matter based on their complete aqueous solubility properties: saccharides, anhydrosaccharides, and secondary oxidation products such as methoxyphenolics and aromatic acids. The sum of these water-soluble compounds ranges from 14 to 89% of TCM for typical samples and is about 40-70% of TCM during an Asian dust episode at the ground stations (11). These water-soluble fractions are unusually high and when coupled with the oxalic and malonic acid contents determined separately (e.g., ref 9) make essentially the total compound mass water-soluble. This is quite different from the urban aerosols such as in Los Angeles, CA or Santiago, Chile, where the bulk of the identified organic compounds are hydrophobic (e.g., refs 25 and 58). It is also different when compared to the Saharan dust 5948
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aerosols from Africa over the North Atlantic which have low contents of these water-soluble compounds (13).
Acknowledgments P.M.M. thanks the Brazilian government (CNPq - Conselho Nacional de Desenvolvimento Cientı´fico e Tecnolo´gico) for financial support (Grant 200330/01-2).
Literature Cited (1) Saxena, P.; Hildemann, L. M. J. Atmos. Chem. 1996, 24, 57-109. (2) Facchini, M. C.; Mircea, M.; Fuzzi, S.; Charlson, R. J. Nature 1999, 401, 257-259. (3) Graham, B.; Mayol-Bracero, O. L.; Guyon, P.; Roberts, G. C.; Decesari, S.; Facchini, M. C.; Artaxo, P.; Maenhaut, W.; Ko¨ll, P.; Andreae, M. O. J. Geophys. Res. 2002, 107 (D20), 8047, doi: 10.1029/2001JD000336, LBA 14/1-16. (4) Delany, A. C.; Zenchelsky, S. Soil Sci. 1976, 121, 146-155. (5) Chester, R. In Nobel Symposium 20, The Changing Chemistry of the Oceans; Dyrssen, D., Jagner, D., Eds.; Wiley: New York, 1972; pp 291-305. (6) Sempe´re´, R.; Kawamura, K. Atmos. Environ. 1994, 28, 449-459. (7) Kawamura, K.; Usukura, K. J. Oceanogr. 1993, 49, 271-283. (8) Kawamura, K.; Sakaguchi, F. J. Geophys. Res. 1999, 104, 35013509. (9) Mochida, M.; Umemoto, N.; Kobayashi, M.; Matsunage, S.; Kawamura, K.; Bates, T. S.; Simoneit, B. R. T. J. Geophys. Res.Atmos. 2003, 108 (D23), 8638, doi: 1029/2002JD003249, ACE 6/1-12. (10) Simoneit, B. R. T.; Schauer, J. J.; Nolte, C. G.; Oros, D. R.; Elias, V. O.; Fraser, M. P.; Rogge, W. F.; Cass, G. R. Atmos. Environ. 1999, 33, 173-182. (11) Simoneit, B. R. T.; Kobayashi, M.; Mochida, M.; Kawamura, K.; Lee, M.; Lim, H.-J.; Turpin, B. J.; Komazaki, Y. J. Geophys. Res. In press. (12) Simoneit, B. R. T. Appl. Geochem. 2002, 17, 129-162. (13) Simoneit, B. R. T.; Elias, V. O. Mar. Chem. 2000, 69, 231-243. (14) Fraser, M. P.; Lakshmanan, K. Environ. Sci. Technol. 2000, 34, 4560-4564. (15) Nolte, C. G.; Schauer, J. J.; Cass, G. R.; Simoneit, B. R. T. Environ. Sci. Technol. 2001, 35, 1912-1919. (16) Zdra´hal, Z.; Oliviera, J.; Vermeylen, R.; Claeys, M.; Maenhaut, W. Environ. Sci. Technol. 2002, 36, 747-753. (17) Sheesley, R. J.; Schauer, J. J.; Chowdhury, Z.; Cass, G. R.; Simoneit, B. R. T. J. Geophys. Res. (Atmos.) 2003, 108 (D9), 4285, doi: 10.1029/2002 JD002981, AAC 8/1-15. (18) Simpson, C. D.; Dills, R. L.; Katz, B. S.; Kalman, D. A. J. Air Waste Manage. Assoc. In press. (19) Hawthorne, S. B.; Miller, D. J.; Barkley, R. M.; Krieger, M. S. Environ. Sci. Technol. 1998, 22, 1191-1196. (20) Oros, D. R.; Simoneit, B. R. T. Appl. Geochem. 2001a, 16, 15131544. (21) Oros, D. R.; Simoneit, B. R. T. Appl. Geochem. 2001b, 16, 15451565. (22) Rogge, W. F.; Hildemann, L. M.; Mazurek, M. A.; Cass, G. R.; Simoneit, B. R. T. Environ. Sci. Technol. 1998, 32, 13-22. (23) Schauer, J. J.; Fraser, M. P.; Cass, G. R.; Simoneit, B. R. T. Environ. Sci. Technol. 2002, 36, 3806-3814. (24) Simoneit, B. R. T.; Rogge, W. F.; Mazurek, M. A.; Standley, L. J.; Hildemann, L. M.; Cass, G. R. Environ. Sci. Technol. 1993, 27, 2533-2541. (25) Didyk, B. M.; Simoneit, B. R. T.; Pezoa L. A.; Riveros M. L.; Flores A. A. Atmos. Environ. 2000, 34, 1167-1179. (26) Simoneit, B. R. T.; Rushdi, A. I.; Otto, A. Oregon State University, 2001; 86pp. (27) Oades, J. M. Geoderma 1993, 56, 377-400. (28) Kolattukudy, P. E. Lipids 1970, 5, 259-275. (29) Rogge, W. F.; Hildemann, L. M.; Mazurek, M. A.; Cass, G. R.; Simoneit, B. R. T. Environ. Sci. Technol. 1993, 27, 2700-2711. (30) Kolattukudy, P. E. Science 1980, 208, 990-1000. (31) Albro, P. W. In Chemistry and Biochemistry of Natural Waxes; Kolattukudy, P. E., Ed.; Elsevier: Amsterdam, 1976; pp 419445. (32) Lechevalier, M. F. CRC Crit. Rev. Microbiol. 1977, 5, 109-210. (33) Martin, F.; Ramstedt, M.; So¨derho¨ll, K.; Canet, D. Plant Physiol. 1988, 86, 935-940. (34) Shaw, N. Adv. Appl. Microbiol. 1974, 17, 63-108. (35) Metting, F. B. In Soil Microbial Ecology; Metting, F. B., Ed.; Marcel Dekker: New York, 1993; pp 3-25. (36) Miltner, A.; Zech, W. Org. Geochem. 1998, 28, 457-463.
(37) Newell, S. Y. In The Fungal Community, 2nd ed.; Caroll, G. C., Wicklow, D. T., Eds.; Marcel Dekker: New York, 1992; pp 521561. (38) Djajakirana, G.; Joergensen, R. G.; Meyer, B. Biol. Fertil. Soils 1996, 22, 299-304. (39) Joergensen, R. G. Soil Biol. Biochem. 2000, 32, 647-652. (40) Ashbaugh, L. L.; Carvacho, O. F.; Brown, M. S.; Chow, J. C.; Watson, J. G.; Magliano, K. C. Atmos. Environ. 2003, 37, 11631173. (41) Rogge, W. F.; Medeiros, P. M.; Simoneit, B. R. T. Atmos. Environ. Manuscript in preparation. (42) Rogge, W. F.; Medeiros, P. M.; Simoneit, B. R. T. Atmos. Environ. Manuscript in preparation. (43) Rogge, W. F.; Medeiros, P. M.; Simoneit, B. R. T. Atmos. Environ. Manuscript in preparation. (44) Kobayashi, M. M.Sc. Thesis, Hokkaido University, Sapporo, Japan, 2002 (in Japanese). (45) Chizhov, O. S.; Molodtsov, N. V.; Kochetkov, N. K. Carbohydr. Res. 1967, 4, 273-276. (46) DeJongh, D. C.; Radford, T.; Hribar, J. D.; Hanessian, S.; Bieber, M.; Dawson, G.; Sweeley, C. C. J. Am. Chem. Soc. 1969, 91, 17281740. (47) Modzeleski, J. E.; Laurie, W. A.; Nagy, B. Geochim. Cosmochim. Acta 1971, 35, 825-838. (48) Pa´ez, M.; Martinez-Castro, I.; Sanz, J.; Olano, A.; Garcia-Raso, A.; Saura-Calixto, F. Chromatographia 1987, 23, 43-46. (49) Martinez-Castro, I.; Pa´ez, M. I.; Sanz, J.; Garcia-Raso, A. J. Chromatogr. 1989, 462, 49-60.
(50) Garcia-Raso, A.; Pa´ez, M. I.; Martinez-Castro, I.; Sanz, J.; Calvo, M. M. J. Chromatogr. 1992, 607, 221-225. (51) Bartolozzi, F.; Bertazza, G.; Bassi, D.; Cristoferi, G. J. Chromatogr. 1987, 758, 99-107. (52) Fiehn, O.; Kopka, J.; Trethewey, R. N.; Willmitzer, L. Anal. Chem. 2000, 72, 3573-3580. (53) Elias, V. O.; Simoneit, B. R. T.; Cordeiro, R. C.; Turcq, B. Geochim. Cosmochim. Acta 2001, 65, 267-272. (54) Nolte, C. G.; Schauer, J. J.; Cass, G. R.; Simoneit, B. R. T. Environ. Sci. Technol. 2002, 36, 4273-4281. (55) Gleixner, G.; Poirier, N.; Bol, R.; Balesdent, J. Organic Geochem. 2002, 33, 357-366. (56) da Cunha, L. C.; Serve, L.; Blazi, J.-L. Organic Geochem. 2002, 33, 953-964. (57) Decesari, S.; Facchini, M. C.; Matta, E.; Lettini, F.; Mircea, M.; Fuzzi, S.; Tagliavini, E.; Putaud, J.-P. Atmos. Environ. 2001, 35, 3691-3699. (58) Schauer, J. J.; Rogge, W. F.; Hildemann, L. M.; Mazurek, M. A.; Cass, G. R.; Simoneit, B. R. T. Atmos. Environ. 1996, 30, 38373855.
Received for review January 2, 2004. Revised manuscript received June 22, 2004. Accepted August 17, 2004. ES0403099
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